Meta-anilide urea compositions and their utility as herbicides

ABSTRACT

Meta-anilide urea compositions have the formula:   IN WHICH X and Y are, independently, oxygen and sulfur; R1 is hydrogen or lower alkyl; R2 and R3 are, independently, hydrogen, alkyl, lower alkoxy, haloalkyl, lower alkenyl, cycloalkyl having from 3 to 6 carbon atoms, inclusive, carbalkoxyalkyl, furfuryl, naphthyl, phenyl or substituted-phenyl, inclusive, in which the substituents are halogen, nitro, or lower alkoxy; R4 is hydrogen or lower alkyl; R5 is hydrogen, alkyl, ethyl cycloalkyl, lower alkenyl, halogenated lower alkyl, cycloalkyl having 3 to 6 carbon atoms, inclusive, pinonoyl 2,4-dichlorophenoxymethylene, benzyl, phenyl, or substituted-phenyl in which the substituents are halogen, nitro, lower alkyl, lower alkoxy or trihalomethyl; Z is halogen, lower alkyl, nitro, amino or trifluoromethyl, and m is an integer having a value from 0 to 4, inclusive, provided that when R1, R2, R3 and R4 are each hydrogen, X and Y are each oxygen and m is O, then R5 is other than methyl or ethyl. The compounds are useful as herbicides and they exhibit both preemergence and post-emergence activity. Representative compounds are: 1-(3&#39;&#39;isobutyramidophenyl)-3-methyl urea, 1-cyclohexyl-3-(3&#39;&#39;propionamidophenyl)urea, 1-butyl-3-(3&#39;&#39;-propionamidophenyl) urea, 1-butyl-3-(3&#39;&#39;-isobutyramidophenyl)urea, 1-(3&#39;&#39;-nitrophenyl)-3-(3&#39;&#39;isobutyramidophenyl) urea, 1-N,N-dimethyl-3(pivalamidophenyl)urea, 1-(3&#39;&#39;-propionamidophenyl)-3-n-butyl thiourea, and 1-(3&#39;&#39;-pentafluoropropionamido phenyl)3,3-dimethyl urea.

[ July 29, 1975 11 META-ANILIDE UREA COMPOSITIONS AND THEIR UTILITY AS IIERBICIDES \[75] lnventor: Eugene G. Teach, El Cerrito, Calif.

[73] Assignee: Stauffer Chemical Company,

Westport, Conn.

\[221 Filed: Feb. 22, 1974 1121] .Appl. No.: 444,630

Related US. Application Data [60] Division of Ser. No. 180,171, Sept. 13, 1971, Pat. No. 3,816,498, which is a division of Ser. No. 23,021, March 26, 1970, Pat. No. 3,642,891, which is a continuation-in-part of Ser. No. 746,007, July 19, 1968, abandoned, which is a continuation-in-part of Ser. No. 662,573, Aug. 23, 1967, abandoned.

[52] US. Cl 260/553 A; 71/70; 71/72; 71/75; 71/88; 71/99; 71/111; 71/120;

260/471 A; 260/552 R; 260/553 C Primary Examiner-R. V. Hines Assistant ExaminerThomas A. Waltz Attorney, Agenl, 0r Firm-Harry A. Pacini; Daniel C. Block; Edwin H. Baker [57] ABSTRACT Meta-anilide urea compositions have the formula:

in which X and Y are, independently, oxygen and sulfur; R is hydrogen or lower alkyl; R and R are, independently, hydrogen, alkyl, lower alkoxy, haloalkyl, lower alkenyl, cycloalkyl having from 3 to 6 carbon atoms, inclusive, earbalkoxyalkyl, furfuryl, naphthyl, phenyl or substituted-phenyl, inclusive, in which the substituents are halogen, nitro, or lower alkoxy; R, is hydrogen or lower alkyl, R is hydrogen, alkyl, ethyl cycloalkyl, lower alkenyl, halogenated lower alkyl, cycloalkyl having 3 to 6 carbon atoms, inclusive, pinonoyl 2,4-dichlorophenoxymethylene, benzyl, phenyl, or substituted-phenyl in which the substituents are halogen, nitro, lower alkyl, lower alkoxy or trihalomethyl; Z is halogen, lower alkyl, nitro, amino or trifluoromethyl, and m is an integer having a value from 0 to 4, inclusive, provided that when R,, R R and R are each hydrogen, X and Y are each oxygen and m is 0, then R is other than methyl or ethyl. The compounds are useful as herbicides and they exhibit both preemergence and post-emergence activity. Representative compounds are: 1-(3'-isobutyramidophenyl)-3- methyl urea, 1 -cyclohexyl-3-( 3 propionamidophenyl )urea, l-butyl-3-( 3 propionam'idophenyl) urea, l-butyl-3-( 3 isobutyramidophenyl)urea, l-( 3 '-nitrophenyl)-3-( 3 isobutyramidophenyl) urea, 1 -N ,N-dimethyl-3- (pivalamidophenyl)urea, l-(3'-propionamidophenyl)- 3-n-butyl thiourea, and l-( 3 '-pentafluoropropionamido phenyl)3,3-dimethyl urea.

17 Claims, N0 Drawings META-ANILIDE UREA COMPOSITIONS AND THEIR UTILITY AS HERBICIDES This is a division of application Ser. No. 180,171, filed Sept. 13, 1971, now US. Pat. No. 3,816,498, which is a division of application Ser. No. 23,021, filed Mar. 26, 1970 now US. Pat. No. 3,642,891, which is a continuation-in-part of application Ser. No. 746,007, filed July 19, 1968, which in turn is a a continuation-inpart of application Ser. No. 662,573, filed Aug. 23, 1967, both now abandoned.

This invention relates to certain novel meta-anilide ureas which are useful as herbicides. More specifically, this invention relates to certain substituted organoanilide ureas and to the preparation and utility of the compounds as herbicides.

The compounds of the present invention correspond to the formula:

in which X and Y are independently selected from the group consisting of oxygen and sulfur, R is hydrogen or lower alkyl, R: and R are independently selected from the group consisting of hydrogen, alkyl, lower alkoxy, haloalkyl, lower alkenyl, cycloalkyl having from 3 to 6 carbon atoms, inclusive, carbalkoxalkyl, furfuryl, naphthyl, phenyl, substituted-phenyl in which said substituents are selected from the group consisting of halogen, nitro, and lower alkoxy; R, is hydrogen or lower alkyl; R is selected from the group hydrogen, alkyl, ethylcycloalkyl, lower alkenyl, halogenated lower alkyl, cycloalkyl having from 3 to 6 carbon atoms, inclusive, pinonoyl, 2,4-dichlorophenoxymethylene, benzyl, phenyl, substituted-phenyl in which said substituents are selected from the group consisting of halogen, nitro, lower alkyl, lower alkoxy and trihalomethyl; and Z is selected from the group consisting of halogen, lower alkyl, nitro, amino and trifluormethyl, and m is an integer having a value from to 4, inclusive, preferably 0 to 2, inclusive, provided that when R R R and R are each hydrogen, X and Y are both oxygen and m is 0, then R is other than methyl or ethyl.

.As employed in this specification, the terms lower alkyl and lower alkoxy preferably include those members of the group containing from 1 to 6 carbon atoms, inclusive, in either a straight chain or a branched chain configuration. Similarly, the term alkyl preferably includes those members of-the group containing 1 to 10 carbon atoms, inclusive. The term lower alkenyl preferably includes those members of the group containing at least one olefinic bond and containing from 2 to 4 carbon atoms, inclusive. The term carbalkoxyalkyl preferably includes those members of the group containing from 3 to 6 carbon atoms, inclusive. The term halogen, as employed herein and in the terms haloalkyl, halogen,

halogenated, trihalomethyl, preferably includes fluorine, chlorine and bromine.

The compounds of the present invention are prepared by several methods. Two such methods applicable in preparing the compounds is the condensation between the appropriate meta-amino substituted anilide with either an isocyanate or carbamoyl chloride and also the condensation of the appropriate meta-amino urea and either an acyl halide or acid anhydride. These methods will be further exemplified below. Similarly, an isothiocyanate is employed to prepare the thiourea derivatives. When the unsubstituted amidophenyl urea is prepared a cyanate salt is reacted with the appropriate substituted amido aniline. The reactions proceed readily in the liquid phase. The employment of a solvent is also useful, facilitating processing, as well as agitation of the reactants. Solvents such as water, benzene, toluene, acetone, tetrahydrofuran, and the like, are employed. A catalyst may be employed to enhance the reaction although a catalyst is not required. Catalysts such as e.g., dibutyltin dilaurate and anhydrous potassium carbonate and copper powder, are effective catalysts. The reactions are carried out at temperatures that permit operation in the liquid phase. These temperatures are between about room temperature and reflux temperature of the solvent if a solvent is employed. Preferably, the reaction mixture is refluxed at an elevated temperature.

Compounds of the present invention are prepared in accordance with the following illustrative examples.

EXAMPLE 1 Preparation of l-(3-isobutyramidophenyl)-3-methyl urea.

Meta-amino isobutyranilide, 12.5g. (0.07 mole), is dissolved in ml. of acetone containing a few drops of dibutyltin dilaurate. Methyl isocyanate, 4.4 g. (0.077 mole), is added to the mixture. The mixture is refluxed for 2 hours. On cooling, the crystalline product is filtered off and dried. There is obtained 8.2 g. (50 percent of theory) of the title compound, m.p. l68-l7lC.

EXAMPLE 2 Preparation of 1-(3-Pivalamidophenyl)-3,3-dimethyl Urea Meta-amino pivalanilide 15.4 g. (0.08 moles) is dissolved in 100 ml. of acetone containing 11 g. of finely powdered anhydrous potassium carbonate and a trace of copper powder. Dimethylcarbamoyl chloride 8.6 g. (0.08 mole) is added and the mixture is refluxed for 8 hours with stirring. The solid is filtered off and the acetone is removed under vacuum. The viscous liquid product is triturated with ether and crystallizes. It is washed with water, and 5% hydrochloric acid solution and is dried. There is obtained 12.5 g. (60 percent of theory) of the title compound, m.p. 18ll86C.

EXAMPLE 3 Preparation of l-(3"propionamidophenyl)-3-n-butyl thiourea.

Meta-propionamidoaniline, 8.2 g. (0.05 mole), is dissolved in 50 ml. of acetone. To this solution is added 5.8 g. of n-butylisothiocyanate. The resulting mixture is refluxed for two hours. After cooling, it is poured on to crushed ice and washed with water. After filtering,

sulfuric acid is added dropwise. The mixture is heated at reflux for 1 hour. The mixture is cooled and the product filtered off. The product is washed successively with dilute (5%) sodium hydroxide, dilute (5%) HCl, 5 and water and then dried. There is obtained l 1.2 g. (68 percent of theory) of the title compound, m.p. 158-l59C.

EXAMPLE 6 Preparation of l-(3'-cyclohexanecarboxamidophenyl)-3-methyl urea N-Meta-aminophenyl-N'-methyl urea 11.5 g. (0.07 mole) dissolved in acetone containing 7.7 g. (0.076 mole) of triethylamine and 1 1.3 g. of cyclohexane carbonyl chloride is added dropwise with stirring. The product precipitates from the acetone and is filtered off, washed with water and then dried. There is obtained 16.0 g. (83 percent of theory) of the title compound, m.p. 190-l93C.

20 The following is a table of the compounds which are prepared according to the aforementioned procedures. Compound numbers have been assigned to them and are used for identification throughout the balance of the specification.

TABLE 1 EXAMPLE 4 Preparation of 3'-propionamidophenyl urea.

Meta-propionamidoaniline, 8.2 g. (9.05 mole) is dissolved in 100 ml. of dilute hydrochloric acid solution.

EXAMPLE 5 Preparation of l-(3-butyramidophenyl)-3-methyl urea.

Compound Number X Y R R2 R3 the product is dried in vacuum. There is obtained 13.8g. (98.5 percent of theory) of the title compound, m.p. l36l38C.

Potassium cyanate, 4.1 g. is dissolved in 20 ml. of water 10 and this is added to the above acid solution. The resulting mixture is maintained at 30-40C. for 3 hours. After cooling, the crystals are filtered and washed with water. They are dried further in vacuum. There is obtained 8.9 g. (86 percent of theory) of the title com- 15 pound, m.p. l88-l90C.

N-Meta-aminophenyl-N-methyl urea, 11.5 g. (0.07 mole) is suspended in 100 ml. of ether and 11.1 g. of n-butyric anhydride containing 5 drops of concentrated.

HHHHHHHHHHHHHHHHHHHHHHHHHHHHHHHHHHHHHHHHHHHHHHH 1 m 1 V. V. v. l n c c n l c n l w m ma a. m m m m m p 6 p 1 m p .w. p .H 1 29 H To a a 1 t 1. 1. .huom mm ..com .h HlJo Hi 0 W h n 3c a c m cm Nc t owhficm c N QC .c "N l t Cxb m mm 2 i wh L w w A EH HME .m 3CC n i C i n c P3 n 3 C C C4 4 n C n c C P3 3 3 Ci 3 C n C C 3 C C CCC n C n C u 3 3 1.1.1.1. HHHH H HHHH C HHHHHHHHHHHHHHHHHHHHHHHHHHHHCHHHHCCCCHHHHHH HHHHHHHHHHHHHHHHHHHHHHHHHHHHHHHHHHHHHHHHHHHHHHH 00000 O O O O OO O O O O O O O0 OO O O0 000 O O O O O OO O O OO O O O OO O O O 0 00000 O O0 000 O OO O O0 O0 OO O O0 000 O0 OO 0 OS S O O O O0 OO O O O O O TABLE I-Continued Compound .Numhcr X Y R H HH H H HHH H HH H H H H HHH H H H HHHH HH H HH HHH HHH H H HHH H HH H H HH HHHHHHHHHHHHHHHHHHHHHHHHHHMWHHHHHHHHHHHHHHHHHHHHH um" HHHHHHHHHHHHHHHHHHHHHHHHHQHHHHHHHHHHHHHHHHHHHHHH 0 O00 000 O 0 000 O O0 000 O0 0 0000 00 0 00 000000 0 0000 0 O0 0 0 00 0 000 000 0 O 000 0 0 0000 00 O 0000 0S 0 00 0000000 0 000 0 00 00 O0 890 234567890 234567890 234 90 4 6 890 2345 44555555 555100660601010 7 1. 77vvn w w obobubnbnomouoobobobg vguvqg Com pound [Number 1% Y R HHHHHHHHHHHHHHHHHHHHHHHHHHHHHH HHHHHHHHHHHHHHHHHHHHHHHHHHHHHH 0 000 0 00 0000 000 00 000 O0 0 0 0 000 0 0 0 0 0 00 0 00 0 0 00 000 0 0 000 00 0 0 0 0 00 0 0 0 67890123456700901234567009)I21J45 1 1 1 1 1 1 1 11 Herbicidal Screening Tests As previously mentioned, the novel compounds herein described are phytotoxic compounds which are useful and valuable in controlling various plants species. Compounds of this invention are tested as herbicides in the following manner.

Pre-emergence herbicide test. On the day preceding treatment, seeds of seven different weed species are planted in individual rows using one species per row across the width of the flat. The seeds used are hairy crabgrass (Digitaria sanguinalis (L) Scop.), yellow foxtail (Selaria glauca (L.) Beauv.), watergrass (Echinochloa crusgalli (L) Beauv.), California red oat {Avena sativa (L.)), redroot pigweed (Amaranthus re- .troflexus (L), lndian mustard (Brassica juncea (L.) Coss.) and curly dock (Rumex crispus (L.). Ample seeds are planted to give about 20 to 50 seedlings per row. after emergence, depending on the size of the plants. The flats are watered after planting. The spraying solution is prepared by dissolving 50 mg. of the test compound in 3 ml. of a solvent, such as acetone, containing l% Tween 20 (polyoxyethylene sorbitan monolaurate). The following day each flat is sprayed at the rate of 20 pounds of the candidate compound per 80 gallons of solution per acre. An atomizer is used to spray the solution on soil surface. The flats are placed in a greenhouse at 80F. and watered regularly. Two weeks later. the degree of weed control is determined by comparing the amount of germination and growth of each weed in the treated flats with weeds in several untreated control flats. The rating system is as follows:

no significant injury (Ol percent control) slight injury (25-35 percent control) 4+ moderate injury (55-65 percent control) il-H- severe injury or death (SS-I00 percent control) An activity index is used to represent the total activity on all seven weed species. It is the sum of the number of plus marks, so that an activity index of 21 represents complete control of all seven weeds. The results of this test are reported in Table II.

Post-emergence herbicide test. Seeds of five weed species including hairy crabgrass, watergrass, wild oats, Indian mustard, and curly dock and one crop pinto beans (Phaseolus vulguris), are planted in flats as described above for preemergence screening. The flats are placed in the greenhouse at 7285F. and watered daily with a sprinkler. About to 14 days after planting when the primary leaves of the bean plant are almost fully expanded and the first trifoliate leaves are just starting to form. the plants are sprayed. The spray is prepared by weighing out 50 mg. of the test compound. dissolving it in 5 ml. of acetone containing l percent Tween lpolyoxy-ethylene sorbitan monolaurate) and then adding 5 ml. of water. The solution is sprayed on the foliage using an atomizer. The spray concentration is 0.5% and the rate would be approximately 20 lb/acre if all of the spray were retained on the plant and the soil, but some spray is lost so it is estimated that the application rate is approximately l2.5 lb/acre.

Beans are used to detect defoliants and plant growth regulators. The beans are trimmed to two or three plants per flat by cutting off the excess weaker plants several days before treatment. The treated plants are placed back in the greenhouse and care is taken to avoid sprinkling the treated foliage with water for three days after treatment. Water is applied to the soil by means of a slow stream from a watering hose taking care not to wet the foliage.

Injury levels are made and recorded 14 days after treatment. The rating system is the same as described above for the pre-emergence test where (-ll-), and (-lll-) are used for the different levels of injury and control. The injury symptoms are also recorded. The maximum activity index for complete control of all the species in the post-emergence screening test is 18 which represents the sum of the plus marks obtained with the six plant species used in the test. The herbicide activity indices are shown in Table II.

TABLE II I-IERBICIDAL ACTIVITY SCREENING RESULTS Compound Number Pre-emergence Post-emergence l l8 l8 2 2 0 3 9 ll 4 21 18 5 16 I8 6 20 I8 7 20 I8 8 13 I5 9 l7 l7 I0 19 l6 ll 21 l8 I2 11 l7 l3 0 8 I4 21 l8 l5 8 l3 l6 6 l4 l7 l6 l6 l8 0 l0 l9 l2 I3 20 0 12 2| 3 0 22 I8 18 23 20 18 24 0 13 26 4 7 27 0 9 28 6 8 29 5 I2 30 l9 l8 3] 19 I8 32 O 8 33 2| [8 34 9 I8 35 0 II 36 21 I8 37 1 IO 38 20 18 39 20 I8 40 l9 I7 41 l7 l6 42 20 I8 43 20 I8 44 20 I7 45 2O 18 46 l8 18 47 l3 18 48 20 I8 49 l9 I6 50 2] 16 SI 20 I8 52 21 I7 53 9 16 54 l2 I8 55 20 I8 56 20 I7 57 l9 17 58 I9 I8 59 l9 I8 60 l5 I8 61 9 I3 62 5 l" 63 0 4 64 l7 I8 65 El 18 66 2t 18 67 8 ll 68 ll 18 69 ll l8 TABLE II-Continued HERBICIDAL ACTIVITY SCREENING RESULTS HERBICIDAL ACTIVITY SCREENING RESULTS Compound Compound Number Pre-emergence Post-emergence Number Pre-emergence Post-emergence 70 18 18 15s 17 17 71 6 13 159 19 17 72 I7 160 21 18 73 5 4 161 2l I8 74 10 I5 10 162 21 I8 75 l7 I8 I63 20 18 7 4 16 164 2l 18 77 I5 18 I65 2] I8 78 9 I8 I66 21 I8 79 5 I4 I67 l8 I8 80 I8 I8 I68 18 I8 8] l9 I8 I69 l8 I8 8 1 11 I5 170 17 16 33 19 I8 171 17 16 a4 14 18 172 17 1s 85 11 I8 173 13 17 86 4 11 174 I8 87 2 11 175 16 18 88 2I I8 176 17 I8 89 0 9 177 17 1a 90 1 11 17s 11 1s 91 7 I4 92 20 I7 "21 85-1007: control of all seven plant species tested pre-emergence. 93 21 I8 85-10071 control of all six plant species tested post-emergence 94 21 95 17 14 :3 {g The new compounds of the present invention are 98 21 18 used as pre-emergence or post-emergence herbicides 99 as I; and are applied in a variety of ways at various concen- 100 1g trations. In ractice, the com ounds are formulated 101 21 p p 102 7 {g with an inert carrier, utilizing methods well-known to :83 g 5 those skilled in the art, thereby making them suitable )5 0 l7 for application as dusts, sprays, or drenches and the :89 I; like in the form and manner required. The mixtures can 0 5 be dis ersed in water with the aid of a wettin a ent or 108 P i g 3 g :3 they can be employed in organic l1qu1d composmons, oil and water, water 1n oil emulsions, with or without Ill l7 l8 112 19 :g the add1t1on of wettmg, dlspersmg or emulsifying Hi g8 18 agents. The amount applied depends upon the nature 115 21 18 of the seeds or plants to be controlled and the rate of H1 g application varies from approximately I to approxi- 118 21 18 mately 50 pounds per acre. One particularly advanta- Hg geous way of applying the compound is a narrow band m |9 3 along a row crop straddling the row. In practice, the

compounds are formulated with an inert carrier utiliz- 124 19 18 ing methods well known to those skilled in the art, :32 :2 :2 thereby making them suitable for particular applica- 127 12 16 128 l9 18 The phytotox1c composmons of this Invention are ap- :%g 13 :3 plied to the plants in the conventional manner. Thus, 13 18 16 the solid and liquid compositions can be applied to the :2 plant by the use of, for example, power-dusters, boom 34 H 16 and hand sprayers and spraydusters. The compositions 135 14 12 can also be applied from airplanes as a dust or a spray g because they are effective in very low dosages. In order 138 3 10 to modify or control growth of germinating seeds or :23 :2 emerging seedlings, as a typical example, the dust and 141 15 16 liquid compositions are applied to the soil according to {2% :2 conventional methods and are preferably distributed in 144 17 14 the soil to a depth of at least one-half inch below the 52 g 6O soil surface. It is not necessary that the phytotoxic com- 47 18 positions be admixed with the soil particles and these :22 compositions can be applied merely by spraying or 50 2 l8 sprmklmg the surface of the soil. The phytotoxic com 151 21 18 positions of this invention can also be applied by addi- 152 21 I8 ,5 tion to irri ation water su lied to the field to be 153 21 1 P 154 2| 18 treated. This method of appllcatlon permits the penetration of the compositions into the soil as the water is 157 I 17 absorbed therein. Dust compositions, granular compo- :sitions or liquid formulations applied to the surface if the soil can be distributed below the surface of the soil by conventional means such as discing, dragging or mixing operations.

The phytotoxic compositions of this invention can also contain other additaments, for example, fertilizers, pesticides and the like, used as adjuvant or in combination with any of the above-described adjuvants. Other phytotoxic compounds useful in combination with the above-describec. compounds include for example, .2,4-dichlorophenoxyacetic acids, 2,4,5-trichlorophenoxyacetic acid, 2-methyl-4-chlorophenoxyacetic acid and the salts, esters and amides thereof; triazine derivatives, such as 2,4-bis (3-methoxypropylamino)- b-methylthio-S-triazine; 2-chloro-4-ethylamino-6-isopropylamino-S-triazine, and 2-ethylamino-4- isopropylamino-6-methylmercapto-S-triazine, urea derivatives, such as 3-(3,4-dichlorophenyl)-l,l-dimethyl urea and 3-(p-chlorophenyl)-l,l-dimethyl urea and acetamides such as N,N diallyl -17-chloroacetamide, .N-(n-chloroacetyl) hexamethylene imine, and N,N-diethyl-a-bromacetamide, and the like; benzoic acids such as 3-amino-2,5-dichlorobenzoic and; thiocarbamates, such as S-propyl dipropylthiocarbamate; S-ethyl-dipropylthiocarbamate, S-ethyl-cyclohexylethyl-thiocarbamate, S-ethyl hexahydro-lH-azepine-lcarbothioate and the like. Fertilizers useful in combination with the active ingredients include for example, ammonium nitrate, urea and superphosphates. Other useful additaments include materials in which plant organisms take root and grow such as compost, manure, humus, sand and the like.

The concentration of a compound of the present invention, constituting an effective amount in the best mode of administration in the utility disclosed is readily determinable by those skilled in the art. Various changes and modifications are possible without departing from the spirit and scope of the invention described herein and will be apparent to those skilled in the art to which it pertains. It is accordingly intended that the present invention shall only be limited by the scope of the claims.

What is claimed is:

l. A compound having the formula in which X and Y are oxygen; R is hydrogen; R is hydrogen or alkyl of l to 10 carbon atoms, R, is cycloalkyl having from 3 to 6 carbon atoms, inclusive, alkyl of l to 10 carbon atoms, or lower alkenyl of 2 to 4 carbon atoms, R, is hydrogen; R is selected from the group hydrogen, alkyl of 1 to 10 carbon atoms, halogenated lower alkyl of 1 to 6 carbon atoms, provided that when R R R and R are hydrogen, X and Y are oxygen and m is 0, then R is other than methyl or ethyl.

2. A compound according to claim 1 in which X and Y are both oxygen, R R and R are each hydrogen, R is cycloalkyl having 3 to 6 carbon atoms, inclusive, R is alkyl, and m is O.

3. A compound according to claim 2 in which R is cyclohexyl and R is ethyl.

4. A compound according to claim 2 in which R is cyclohexyl and R is tert-butyl.

5. A compound according to claim 2 in which R is cyclohexyl and R is l,l-dimethylbutyl.

6. A compound according to claim 1 in which X and Y and both oxygen, R, and R are each hydrogen, R R and R are each alkyl, and m is 0.

7. A compound according to claim 6 in which R is methyl, R is methyl and R is tert-butyl.

8. A compound according to claim 6 in which R is methyl, R is methyl and R is n-propyl.

9. A compound according to claim 1 in which X and Y are each oxygen, R, and R are each hydrogen, R and R are each alkyl, R is a halogenated lower alkyl and m is 0. r

10. A compound according to claim 9 in which R is methyl, R is methyl, and R is trichloromethyl.

11. A compound according to claim 9 in which R is methyl, R is methyl and R is trifluoromethyl.

12. A compound according to claim 9 in which R is methyl, R is methyl and R is pentafluoroethyl.

13. A compound according to claim 1 in which X and Y are each oxygen, R R and R are each hydrogen, R is lower alkenyl, R is alkyl and m is 0.

14. A compound according to claim 12 in which R; is allyl and R is tert-butyl.

15. A compound according to claim 12 in which R: is allyl and R is l-methylbutyl.

16. A compound according to claim 12 in which R; is allyl and R is 1,1-dimethylbutyl.

17. A compound according to claim 12 in which R is allyl and R is isopropyl. 

1. A COMPOUND HAVING THE FORMULA
 2. A compound according to claim 1 in which X and Y are both oxygen, R1, R2 and R4 are each hydrogen, R3 is cycloalkyl having 3 to 6 carbon atoms, inclusive, R5 is alkyl, and m is
 0. 3. A compound according to claim 2 in which R3 is cyclohexyl and R5 is ethyl.
 4. A compound according to claim 2 in which R3 is cyclohexyl and R5 is tert-butyl.
 5. A compound according to claim 2 in which R3 is cyclohexyl and R5 is 1,1-dimethylbutyl.
 6. A compound according to claim 1 in which X and Y and both oxygen, R1 and R4 are each hydrogen, R2, R3 and R5 are each alkyl, and m is
 0. 7. A compound according to claim 6 in which R2 is methyl, R3 is methyl and R5 is tert-butyl.
 8. A compound according to claim 6 in which R2 is methyl, R3 is methyl and R5 is n-propyl.
 9. A compound according to claim 1 in which X and Y are each oxygen, R1 and R4 are each hydrogen, R2 and R3 are each alkyl, R5 is a halogenated lower alkyl and m is
 0. 10. A compound according to claim 9 in which R2 is methyl, R3 is methyl, and R5 is trichloromethyl.
 11. A compound according to claim 9 in which R2 is methyl, R3 is methyl and R5 is trifluoromethyl.
 12. A compound according to claim 9 in which R2 is methyl, R3 is methyl and R5 is pentafluoroethyl.
 13. A compound according to claim 1 in which X and Y are each oxygen, R1, R2 and R4 are each hydrogen, R3 is lower alkenyl, R5 is alkyl and m is
 0. 14. A compound according to claim 12 in which R3 is allyl and R5 is tert-butyl.
 15. A compound according to claim 12 in which R3 is allyl and R5 is 1-methylbutyl.
 16. A compound according to claim 12 in which R3 is allyl and R5 is 1,1-dimethylbutyl.
 17. A compound according to claim 12 in which R3 is allyl and R5 is isopropyl. 